TW201622867A - Solder material, solder joint, and production method for solder material - Google Patents

Solder material, solder joint, and production method for solder material Download PDF

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Publication number
TW201622867A
TW201622867A TW104128294A TW104128294A TW201622867A TW 201622867 A TW201622867 A TW 201622867A TW 104128294 A TW104128294 A TW 104128294A TW 104128294 A TW104128294 A TW 104128294A TW 201622867 A TW201622867 A TW 201622867A
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TW
Taiwan
Prior art keywords
solder
less
layer
sno
film
Prior art date
Application number
TW104128294A
Other languages
Chinese (zh)
Other versions
TWI543835B (en
Inventor
Hiroyoshi Kawasaki
Takahiro Roppongi
Daisuke Soma
Isamu Sato
Yuji Kawamata
Original Assignee
Senju Metal Industry Co
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Publication date
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Publication of TW201622867A publication Critical patent/TW201622867A/en
Application granted granted Critical
Publication of TWI543835B publication Critical patent/TWI543835B/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/365—Selection of non-metallic compositions of coating materials either alone or conjoint with selection of soldering or welding materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C8/10—Oxidising
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    • H01L2224/13099—Material
    • H01L2224/131—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/13138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
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    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
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    • H01L2224/1354—Coating
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    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/1354—Coating
    • H01L2224/13575—Plural coating layers
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    • H01L2224/1354—Coating
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Abstract

Provided is a solder material configured so that it is possible to minimize the growth of an oxide film. The solder material is a solder ball 1A configured from a solder layer 2 and a coating layer 3 that covers the solder layer 2. The solder layer 2 has a spherical shape and is configured from a metal material comprising an alloy in which the Sn content is 40% or more. The solder layer 2 is alternatively configured from a metal material in which the Sn content is 100%. The coating layer 3 comprises a SnO film 3a that is formed on the outside of the solder layer 2 and a SnO2 film 3b that is formed on the outside of the SnO film 3a. The thickness of the coating layer 3 is greater than 0 nm and preferably equal to or less than 4.5 nm. In addition, the yellowness of the solder ball 1A is preferably 5.7 or less.

Description

焊接材料、焊接接頭以及焊接材料之製造方法 Welding material, welded joint, and manufacturing method of welding material

本發明為有關於以Sn作為主成分的焊接材料、焊接接頭以及焊接材料的製造方法。 The present invention relates to a method of producing a solder material, a solder joint, and a solder material using Sn as a main component.

近年來，由於小型情報機器的發達，其所搭載的電子元件急速地小型化正進行著。電子元件為了小型化的需求，而對應連接端子的窄小化或封裝面積的縮小化，可適用背面設置著電極的球柵陣列(ball grid array，以下稱為「BGA」)。 In recent years, due to the development of small-sized information devices, the electronic components mounted on them have been rapidly miniaturized. In order to miniaturize the electronic component, the ball grid array (hereinafter referred to as "BGA") may be applied to the narrowing of the connection terminal or the reduction in the package area.

適用BGA的電子元件例如有半導體封裝。半導體封裝為將含有電極的半導體晶片以樹脂密封。在半導體晶片的電極上，形成焊料凸塊。此焊料凸塊可藉由將焊球接合於半導體晶片的電極而形成。適用BGA的半導體封裝置於印刷電路板上，使得各焊料凸塊與印刷電路板的導電性連接盤(land)接觸，藉由加熱而熔融的焊料凸塊與連接盤接合，而搭載於印刷電路板。 Electronic components suitable for BGA are, for example, semiconductor packages. The semiconductor package is to seal the semiconductor wafer containing the electrodes with a resin. Solder bumps are formed on the electrodes of the semiconductor wafer. The solder bumps can be formed by bonding solder balls to the electrodes of the semiconductor wafer. A semiconductor package suitable for BGA is placed on a printed circuit board such that each solder bump is in contact with a conductive land of the printed circuit board, and the solder bump which is melted by heating is bonded to the land and mounted on the printed circuit board.

那麼，為了將焊球接合於電極，需要抑制焊球的表面形成金屬氧化膜。再者，混合焊球與助焊劑(flux)，而作為焊膏(solder paste)使用時，需要抑制保存時的黏度上昇。 Then, in order to bond the solder balls to the electrodes, it is necessary to suppress the formation of a metal oxide film on the surface of the solder balls. Further, when solder balls and flux are mixed, when used as a solder paste, it is necessary to suppress an increase in viscosity during storage.

在此，焊球表面上形成的氧化膜的膜厚與黃色度有比例關係。於是，使用黃色度在預定值以下，亦即，使用氧 化膜在預定值以下的焊球，藉由加熱破壞氧化膜使焊球能結合的技術(例如，參照專利文獻1)被提出。此專利文獻1中揭示：首先，挑選在製造後表面的黃化度成為10以下的焊球，藉由嚴密地管理保存狀態而防止焊球表面的黃化，即，抑制焊球表面的SnO氧化膜成長的同時，使用此焊球形成的焊料凸塊之表面，形成SnO氧化膜以及SnO2氧化膜。 Here, the film thickness of the oxide film formed on the surface of the solder ball is proportional to the yellowness. Then, a technique in which the yellowness is equal to or less than a predetermined value, that is, a solder ball having an oxide film of a predetermined value or less, and the solder ball is bonded by heating to break the oxide film (for example, refer to Patent Document 1) is proposed. Patent Document 1 discloses that, first, a solder ball having a yellowing degree of 10 or less on the surface after the production is selected, and the yellowing of the surface of the solder ball is prevented by strictly managing the storage state, that is, the SnO oxidation on the surface of the solder ball is suppressed. At the same time as the film grows, the surface of the solder bump formed by the solder ball is used to form a SnO oxide film and a SnO 2 oxide film.

再者，在焊球的表面上形成預定值的氧化膜，並可抑制黏度上昇的技術(例如，參照專利文獻2)被提出。此專利文獻2中揭示：可抑制在焊接粒子表面形成以SnO或SnO2為主成分之氧化錫構成的氧化覆膜，且與助焊劑混合．攪拌而製造的焊膏製造後經過時間造成的黏度上昇。 Further, a technique of forming an oxide film of a predetermined value on the surface of the solder ball and suppressing an increase in viscosity (for example, refer to Patent Document 2) has been proposed. Patent Document 2 discloses that an oxide film composed of tin oxide containing SnO or SnO 2 as a main component on the surface of the solder particles can be suppressed and mixed with the flux. The viscosity of the solder paste produced by stirring is increased after the elapse of time.

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1：特開2009-248156號公報 Patent Document 1: JP-A-2009-248156

專利文獻2：特許第4084657號公報 Patent Document 2: Patent No. 4084657

以Sn作為主成分的焊球，其Sn與空氣中的O2反應而形成SnO膜。此膜厚增加時，焊接時助焊劑的除去變得困難，焊球的表面上殘留氧化膜時，潤濕性變差。再者，一旦氧化膜厚增加時，黃色度上昇。有時利用黃色度作為焊球的外觀檢查，若不能抑制氧化膜厚的增加，焊球被判斷為不適合使用的可能性變高。 A solder ball containing Sn as a main component, Sn reacts with O 2 in the air to form a SnO film. When the film thickness is increased, the removal of the flux during soldering becomes difficult, and when the oxide film remains on the surface of the solder ball, the wettability is deteriorated. Further, as the thickness of the oxide film increases, the yellowness rises. In some cases, the yellowness is used as an appearance check of the solder ball, and if the increase in the thickness of the oxide film cannot be suppressed, the possibility that the solder ball is judged to be unsuitable for use becomes high.

專利文獻1因為嚴密地管理保存狀態，可抑制焊球表面的SnO氧化膜的成長。再者，專利文獻1著眼於結晶質的SnO2氧化膜，因伴隨焊球的溶融之內部變形而容易破損，使焊料與電極端子的接合性改善，但在保存狀態的管理以外，完全沒有揭示以氧化膜的組成而抑制氧化膜的成長。更進一步地說，關於專利文獻2，完全沒有揭示關於抑制SnO氧化膜的成長。 In Patent Document 1, since the storage state is strictly controlled, the growth of the SnO oxide film on the surface of the solder ball can be suppressed. In addition, Patent Document 1 focuses on a crystalline SnO 2 oxide film, which is easily broken by internal deformation due to melting of the solder ball, and improves the bondability between the solder and the electrode terminal. However, the management of the storage state is not disclosed at all. The growth of the oxide film is suppressed by the composition of the oxide film. Further, regarding Patent Document 2, there is no disclosure about suppressing the growth of the SnO oxide film.

於是，本發明可抑制氧化膜的成長，並因此，提供保存性及潤濕性良好的焊接材料，焊接接頭及焊接材料的製造方法為目的。 Therefore, the present invention can suppress the growth of the oxide film, and therefore, it is intended to provide a solder material having good storage stability and wettability, a solder joint, and a method for producing a solder material.

本發明者們發現以Sn為主成分的焊接層，藉由覆蓋含有SnO及SnO2的覆蓋層，可抑制氧化膜的成長。又，含有SnO及SnO2的覆蓋層係表示以SnO為主成分的由氧化錫構成之氧化覆膜層，以及，以SnO2為主成分的由氧化錫構成之氧化覆膜層。在以下的說明中也一樣。 The present inventors have found that a solder layer containing Sn as a main component can suppress the growth of an oxide film by covering a coating layer containing SnO and SnO 2 . Further, the coating layer containing SnO and SnO 2 is an oxide film layer made of tin oxide containing SnO as a main component, and an oxide film layer made of tin oxide containing SnO 2 as a main component. The same is true in the following description.

申請專利範圍第1項記載的發明為一種焊接材料，其包括：焊接層，由Sn含量為40%以上的合金構成的金屬材料或是由Sn含量為100%的金屬材料構成；以及覆蓋層，覆蓋上述焊接層表面之直徑1~1000μm的球體，覆蓋層為在上述焊接層的外側形成SnO膜、在SnO膜的外側形成SnO2膜，覆蓋層的厚度為大於0nm、4.5nm以下。 The invention described in claim 1 is a solder material comprising: a solder layer, a metal material composed of an alloy having a Sn content of 40% or more, or a metal material having a Sn content of 100%; and a cover layer, The spherical body having a diameter of 1 to 1000 μm covering the surface of the solder layer is formed by forming a SnO film on the outer side of the solder layer and a SnO 2 film on the outer side of the SnO film. The thickness of the cover layer is greater than 0 nm and 4.5 nm.

申請專利範圍第2項所述之發明為，如申請專利範圍第1項所述之焊接材料中，在L*a*b*表色系統中的黃色 度為5.7以下。 The invention described in claim 2 is yellow in the L*a*b* color system as in the welding material described in claim 1 The degree is 5.7 or less.

申請專利範圍第3項記載的發明為一種焊接材料，包括：焊接層，由Sn的含量為40%以上的合金所構成的金屬材料或由Sn的含量為100%的金屬材料所構成的；以及覆蓋層，覆蓋焊接層表面之直徑1~1000μm的球體，覆蓋層為在焊接層的外側形成SnO膜、在上述SnO膜的外側形成SnO2膜，且該焊接材料的L*a*b*表色系統中的黃色度為5.7以下。 The invention described in claim 3 is a solder material comprising: a solder layer, a metal material composed of an alloy having a Sn content of 40% or more, or a metal material having a Sn content of 100%; The cover layer covers a sphere having a diameter of 1 to 1000 μm on the surface of the solder layer, the cover layer is a SnO film formed on the outer side of the solder layer, and the SnO 2 film is formed on the outer side of the SnO film, and the L*a*b* color of the solder material The yellowness in the system is 5.7 or less.

申請專利範圍第4項記載的發明為，如申請專利範圍第1~3項中任一項所述之焊接材料，其中焊接層含有Ag為0%以上、小於4%，Cu為0%以上、小於1%、P為0ppm以上、小於5ppm、Ge為0ppm以上、小於20ppm。 The welding material according to any one of claims 1 to 3, wherein the welding layer contains Ag of 0% or more, less than 4%, and Cu of 0% or more. Less than 1%, P is 0 ppm or more, less than 5 ppm, and Ge is 0 ppm or more and less than 20 ppm.

申請專利範圍第5項記載的發明為，如申請專利範圍第1~4項中任一項所述之焊接材料，其中焊接層使Sn含量成為40%以上，(i)從Ni、Co、Fe、Sb之中選擇至少一個元素，使其含有整體為1%以下或者是各別元素為小於1%，以及，從In、Bi選擇至少一個以上元素，使其含有整體為40%以下，或者是In、Bi其中一個元素為小於40%，另一個元素為小於20%，或者是：(ii)從Ni、Co、Fe、Sb之中選擇至少一個元素，使其含有整體為小於1%，或者是各別元素為小於1%，或是，從In、Bi之中選擇至少一個以上元素，使其含有整體為小於40%或者是In、Bi其中一個元素為小於40%，另一個元素為小於20%。 The invention according to any one of claims 1 to 4, wherein the solder layer has a Sn content of 40% or more, (i) from Ni, Co, Fe. And selecting at least one element from Sb such that the total content is 1% or less or the individual elements are less than 1%, and at least one or more elements are selected from In and Bi so as to contain 40% or less as a whole, or One of In, Bi is less than 40%, the other element is less than 20%, or: (ii) at least one element selected from Ni, Co, Fe, Sb, such that it contains less than 1% overall, or The individual elements are less than 1%, or at least one or more elements are selected from In and Bi, such that the total content is less than 40% or In, Bi is one element less than 40%, and the other element is less than 20%.

申請專利範圍第6項記載的發明為，申請專利範圍第1~5項中任一項所述之焊接材料，其中放射的α線量為 0.0200cph/cm2以下。 The invention described in claim 6 is the welding material according to any one of claims 1 to 5, wherein the amount of α-ray emitted is 0.0200 cph/cm 2 or less.

申請專利範圍第7項記載的發明為，一種焊接接頭，其特徵在於使用如申請專利範圍第1~6項中任一項所述之焊接材料而得到。 The invention described in claim 7 is a welded joint obtained by using the welding material according to any one of claims 1 to 6.

申請專利範圍第8項記載的發明為，一種焊接材料的製造方法，其特徵在於包括：由Sn含量為40%以上的合金構成的金屬材料或是由Sn含量為100%的金屬材料構成的焊接層之焊接層的形成步驟；以及在上述焊接層的外側形成SnO膜、在上述SnO膜的外側形成SnO2膜之包含厚度大於0nm、4.5nm以下的覆蓋層形成於焊接層的表面的氧化膜的形成步驟，以製造直徑為1~1000μm的球體。 The invention according to claim 8 is a method for producing a solder material, which comprises a metal material composed of an alloy having a Sn content of 40% or more or a metal material having a Sn content of 100%. the step of forming the solder layer of the layer; and forming a film of SnO outside of the solder layer, forming a film of SnO 2 SnO outside of the film thickness of oxide film 0nm, 4.5nm or less coating layer formed on the surface of the solder layer comprises The forming step is to fabricate a sphere having a diameter of 1 to 1000 μm.

申請專利範圍第9項記載的發明為，如申請專利範圍第8項所述之焊接材料的製造方法，其中在上述氧化膜形成步驟，形成覆蓋層表面的L*a*b*表色系統中黃色度為5.7以下。 The invention of claim 9 is the method for producing a solder material according to claim 8, wherein in the step of forming the oxide film, the L*a*b* color system of the surface of the cover layer is formed. The yellowness is 5.7 or less.

申請專利範圍第7項記載的發明為，如申請專利範圍第8項或第9項所述之焊接材料的製造方法，其中在上述氧化膜的形成步驟，照射O2-Ar電漿(plasma)於上述焊接層的表面。 The invention of claim 7 is the method for producing a solder material according to the eighth or the ninth aspect of the invention, wherein the oxide film is irradiated with O 2 -Ar plasma (plasma) On the surface of the above solder layer.

於本發明，將焊接層覆蓋的覆蓋層中，在SnO膜的外側形成SnO2膜時，可抑制Sn與空氣中的O2的反應，而抑制SnO膜及SnO2膜的成長，可抑制膜厚的增加，再者，藉由抑制膜厚的增加，可抑制黃變，並可抑制L*a*b*表色系統 中的黃色度在5.7以下。因此，能提供保存性及潤濕性良好的焊接材料，以及，使用此焊接材料的焊接接頭。 In the present invention, when the SnO 2 film is formed on the outer side of the SnO film in the coating layer covered with the solder layer, the reaction between Sn and O 2 in the air can be suppressed, and the growth of the SnO film and the SnO 2 film can be suppressed, and the film can be suppressed. The thickness is increased, and further, by suppressing the increase in film thickness, yellowing can be suppressed, and the yellowness in the L*a*b* color system can be suppressed to be 5.7 or less. Therefore, it is possible to provide a welding material having good storage stability and wettability, and a welded joint using the welding material.

1A‧‧‧焊球 1A‧‧‧ solder balls

2‧‧‧焊接層 2‧‧‧welding layer

3‧‧‧覆蓋層 3‧‧‧ Coverage

3a‧‧‧SnO膜 3a‧‧‧SnO film

3b‧‧‧SnO2膜 3b‧‧‧SnO 2 film

第1圖為顯示作為本實施形態的焊接材料之一例的焊球的示意構造的剖面圖。 Fig. 1 is a cross-sectional view showing a schematic structure of a solder ball as an example of a solder material of the present embodiment.

第2A圖為顯示作為本實施形態的焊接材料之一例的焊球製造方法的示意剖面圖。 Fig. 2A is a schematic cross-sectional view showing a method of manufacturing a solder ball as an example of a solder material of the embodiment.

第2B圖為顯示作為本實施形態的焊接材料之一例的焊球製造方法的示意剖面圖。 Fig. 2B is a schematic cross-sectional view showing a method of manufacturing a solder ball as an example of the solder material of the embodiment.

第2C圖為顯示作為本實施形態的焊接材料之一例的焊球製造方法的示意剖面圖。 Fig. 2C is a schematic cross-sectional view showing a method of manufacturing a solder ball as an example of the solder material of the embodiment.

以下對於本發明的焊接材料、焊接接頭及焊接材料的製造方法進行說明。 Hereinafter, the welding material, the welded joint, and the method of producing the welding material of the present invention will be described.

〈焊接材料的構成例〉 <Configuration Example of Welding Material>

第1圖為顯示作為本實施形態的焊接材料之一例的焊球示意剖面圖。又，在本說明書中，關於焊接材料的組成之單位(ppm及ppb)若並無特別指定時表示對質量的比例(質量ppm、質量ppb及質量%)。 Fig. 1 is a schematic cross-sectional view showing a solder ball as an example of a solder material of the present embodiment. In addition, in the present specification, the unit (ppm and ppb) of the composition of the solder material indicates the ratio of mass to mass (mass ppm, mass ppb, and mass%) unless otherwise specified.

本實施形態的焊球1A由焊接層2以及覆蓋焊接層2的覆蓋層3構成。焊接層2為球狀，且由0%以上、小於4%的Ag、0%以上、小於1%的Cu、Sn含量40%以上的合金構成。通常，雖然添加了預定量的P或Ge而增進了抗氧化性，但在 本發明中不添加這些也可增進抗氧化性。不過，在本發明中即使添加小於5ppm的P，添加小於20ppm的Ge，也不會損及本發明的效果。因此，即使不添加P或Ge也可以，若要添加的話，使P的添加量在小於5ppm，Ge的添加量為小於20ppm，所以，使P的添加量在0ppm以上、小於5ppm，Ge的添加量在0ppm以上、小於20ppm。 The solder ball 1A of the present embodiment is composed of a solder layer 2 and a cover layer 3 covering the solder layer 2. The solder layer 2 is spherical and composed of 0% or more, less than 4% of Ag, 0% or more, less than 1% of Cu, and an alloy having a Sn content of 40% or more. Usually, although a predetermined amount of P or Ge is added to enhance oxidation resistance, The addition of these in the present invention also enhances the oxidation resistance. However, in the present invention, even if less than 5 ppm of P is added, addition of less than 20 ppm of Ge does not impair the effects of the present invention. Therefore, even if P or Ge is not added, if the amount of addition of P is less than 5 ppm and the amount of addition of Ge is less than 20 ppm, the addition amount of P is 0 ppm or more and less than 5 ppm, and addition of Ge is added. The amount is 0 ppm or more and less than 20 ppm.

再者，焊接層2為使Sn的含量成為40%以上的方式，從Ni、Co、Fe、Sb之中選擇至少一個元素，使其含有整體為小於1%，或者是各別元素為小於1%，以及，從In、Bi之中選擇至少一個以上元素，使其含有整體為小於40%，或是In、Bi其中一個元素為小於40%，另一個元素為小於20%。 Further, the solder layer 2 is formed so that the content of Sn is 40% or more, and at least one element is selected from Ni, Co, Fe, and Sb so as to contain less than 1% as a whole or less than 1 each element. %, and, at least one or more elements selected from In and Bi are made to contain less than 40% in total, or one of In and Bi is less than 40%, and the other element is less than 20%.

或者是，從Ni、Co、Fe、Sb之中選擇至少一個元素，使其含有整體為小於1%或各別元素為小於1%，或是，從In、Bi之中選擇至少一個以上元素，使其含有整體為小於40%，或是In、Bi其中一個元素為小於40%，另一個元素為小於20%。 Alternatively, at least one element selected from Ni, Co, Fe, and Sb is contained in an amount of less than 1% as a whole or less than 1% in each element, or at least one element is selected from In and Bi. It is made to contain less than 40% in total, or one of In and Bi is less than 40%, and the other element is less than 20%.

更進一步地，焊接層2由Sn含量為100%的金屬材料構成也可以，又，以從焊接層2放射的α射線量在0.0200cph/cm2以下的材料較佳。 Further, the solder layer 2 may be composed of a metal material having a Sn content of 100%, and a material having an amount of α-rays radiated from the solder layer 2 of 0.0200 cph/cm 2 or less is preferable.

覆蓋層3為，在焊接層2的外側形成SnO膜3a，並在SnO膜3a的外側形成SnO2膜3b。焊球1A因接觸空氣，在焊球層2的表面形成的SnO層將隨著時間的經過而變厚。再者，若膜厚變厚，焊球1A的表面將發生黃變。 In the cover layer 3, the SnO film 3a is formed on the outer side of the solder layer 2, and the SnO 2 film 3b is formed on the outer side of the SnO film 3a. The solder ball 1A is exposed to the air, and the SnO layer formed on the surface of the solder ball layer 2 will become thicker as time passes. Further, if the film thickness is increased, the surface of the solder ball 1A will be yellowed.

相對於此，若在焊接層2的外側形成SnO膜3a， Sn與空氣中的O2的反應受到抑制，並且SnO膜3a及SnO2膜3b本身的成長也受到抑制的關係，造成膜厚的增加受到了抑制的結果。再者，因為膜厚的增加受到抑制，黃變受到抑制，使得構成焊接層2的金屬材料可保持既有的銀白色。 On the other hand, when the SnO film 3a is formed on the outer side of the solder layer 2, the reaction between Sn and O 2 in the air is suppressed, and the growth of the SnO film 3a and the SnO 2 film 3b itself is also suppressed, resulting in a film thickness. The increase is suppressed. Furthermore, since the increase in film thickness is suppressed, the yellowing is suppressed, so that the metal material constituting the solder layer 2 can maintain the existing silver white.

焊球1A以1~1000μm直徑較佳，再者，覆蓋層3的厚度以大於0nm(表示不包含0nm)、4.5nm以下較佳。覆蓋層3的厚度若超過4.5nm，焊接時以助焊劑進行覆蓋層3的去除變得困難，而使濕潤性變差。 The solder ball 1A is preferably 1 to 1000 μm in diameter, and further, the thickness of the cover layer 3 is preferably greater than 0 nm (indicating that 0 nm is not included) and 4.5 nm or less. When the thickness of the cover layer 3 exceeds 4.5 nm, it is difficult to remove the cover layer 3 with a flux during soldering, and the wettability is deteriorated.

再者焊球1A的黃色度b*以5.7以下較佳，在管理製造、保存焊球1A時，會有利用黃色度的情形。這是因為所謂黃色度高，表示SnO的膜厚較厚，黃色度超過既定值的焊球，會被當作不適合使用者而可以排除。 Further, the yellowness b* of the solder ball 1A is preferably 5.7 or less, and when the solder ball 1A is managed and stored, the yellowness may be utilized. This is because the so-called yellowness is high, indicating that the film thickness of SnO is thick, and the solder ball having a yellowness exceeding a predetermined value can be excluded as being unsuitable for the user.

亮度及黃色度以使用KONICA MINOLTA製CM-3500d2600d型分光光度計，以D65光源、10度的視野並以JIS Z 8722「顏色的測定方法-反射及透射物體」為準則測定分光穿透率，從色彩值(L*、a*、b*)而求得。 The brightness and the yellowness were measured by using a CM-3500d2600d spectrophotometer manufactured by KONICA MINOLTA, using a D65 light source, a field of view of 10 degrees, and measuring the spectral transmittance according to JIS Z 8722 "Method for measuring color - reflecting and transmitting objects". The color values (L*, a*, b*) are obtained.

又，色彩值(L*、a*、b*)為如同JIS Z 8729「顏色的表示方法-L*a*b*表色系統及L*U*V*表色系統」中的規定。 Further, the color values (L*, a*, b*) are as defined in JIS Z 8729 "Color Expression Method - L*a*b* Color System and L*U*V* Color System".

又，焊接材料的形狀雖然在本例為球狀，然而也可以為圓筒狀、四角柱狀等其他的形狀。再者，從焊球1A放射的α射線也以在0.0200cph/cm2以下者較佳。 Further, although the shape of the welding material is spherical in this example, it may be other shapes such as a cylindrical shape or a quadrangular prism shape. Further, the α-ray emitted from the solder ball 1A is also preferably 0.0200 cph/cm 2 or less.

〈焊接材料的製造方法例〉 <Example of Manufacturing Method of Welding Material>

第2A圖、第2B圖及第2C圖為表示作為本實施形態的焊接材料之一例的焊球的製造方法的示意剖面圖。 2A, 2B, and 2C are schematic cross-sectional views showing a method of manufacturing the solder ball as an example of the solder material of the embodiment.

形成焊接層的步驟如第2A圖所示，以上述從Sn含量40%以上的合金構成的金屬材料，或是以Sn含量為100%的金屬材料，形成球狀的焊接層2。形成焊接層的步驟在本例中使用將熔融的金屬材料滴下硬化成為球狀的滴下法。 The step of forming the solder layer is as shown in FIG. 2A, and the spherical solder layer 2 is formed of the above-described metal material composed of an alloy having a Sn content of 40% or more or a metal material having a Sn content of 100%. The step of forming the solder layer is a dropping method in which the molten metal material is dripped and hardened into a spherical shape in this example.

形成氧化膜的步驟，如第2B圖所示，在焊接層2的表面因接觸空氣產生的SnO膜3a，如第2C圖所示，形成SnO2膜3b。氧化膜形成的方法，可使用一般已知的方法。例如，可列舉氣相沈積法、濺鍍法、電漿照射法等方法。在本例中，形成氧化膜的步驟，使用已知的大氣電漿裝置以電漿照射法實施，電漿照射法係將熔融金屬從滴下至硬化的期間，以高濃度的O2-Ar電漿照射。 In the step of forming the oxide film, as shown in Fig. 2B, the SnO 2 film 3b is formed on the surface of the solder layer 2 by the contact with the SnO film 3a generated by the air, as shown in Fig. 2C. As the method of forming the oxide film, a generally known method can be used. For example, methods such as a vapor deposition method, a sputtering method, and a plasma irradiation method can be mentioned. In this example, the step of forming an oxide film is carried out by a plasma irradiation method using a known atmospheric plasma device, which is a high concentration of O 2 -Ar during the period from the dropping to the hardening of the molten metal. Plasma irradiation.

根據以上的製造方法，可製造在含有既定直徑的焊接層2的表面，形成有覆蓋層3的焊球1A。覆蓋層3a為厚度大於0nm、4.5nm以下，且在焊接層2的外側形成SnO膜3a、SnO膜3a的外側形成SnO2膜3b。再者，焊球的黃色度為5.66以下。 According to the above manufacturing method, the solder ball 1A in which the coating layer 3 is formed on the surface of the solder layer 2 having a predetermined diameter can be manufactured. The cover layer 3a has a thickness of more than 0 nm and 4.5 nm or less, and an SnO 2 film 3b is formed outside the Sn2 film 3a and the SnO film 3a on the outside of the solder layer 2. Furthermore, the yellowness of the solder ball is 5.66 or less.

〈實施例〉 <Example>

以Ag 3%、Cu 0.5%，剩餘部份由Sn構成的金屬材料，根據滴下法製造相當於焊接層2的金屬球，此金屬球以電漿照射法形成相當於覆蓋層3的覆膜，生成實施例的焊球。電漿照射法為熔融的金屬材料至滴下的期間，照射高濃度的O2-Ar電漿。 A metal ball corresponding to the solder layer 2 is produced by a dropping method of Ag 3%, Cu 0.5%, and a metal material composed of Sn, and the metal ball is formed into a coating film corresponding to the cover layer 3 by a plasma irradiation method. The solder balls of the examples were produced. The plasma irradiation method is a period in which the molten metal material is dropped, and a high concentration of O 2 -Ar plasma is irradiated.

在表面以自然氧化形成SnO層而生成焊球，作為比較例。 A SnB layer was formed by natural oxidation on the surface to form a solder ball as a comparative example.

實施例與比較例的焊球以200℃加熱，以黃色度 b*的值，觀察氧化行為的結果如表1所示。 The solder balls of the examples and the comparative examples were heated at 200 ° C in yellow The values of b* and the results of observing the oxidation behavior are shown in Table 1.

如表1所示，相對於比較例的焊球快速上升的黃色度b*的值，實施例的焊球根據連續電化學還原法(SERA，Sequential Electrochemical Reduction Analysis)的定性分析，可得知藉由以Sn作為主成份的焊接層的外側形成SnO層、SnO層的外側形成SnO2層，可抑制氧化膜厚的成長。 As shown in Table 1, with respect to the value of the yellowness b* of the solder ball rising rapidly in the comparative example, the solder ball of the example can be known by the qualitative analysis of the Sequential Electrochemical Reduction Analysis (SERA). The SnO layer is formed on the outer side of the solder layer containing Sn as a main component, and the SnO 2 layer is formed on the outer side of the SnO layer, whereby the growth of the oxide film thickness can be suppressed.

再者，為了作為參考，比較例中因分離氧化步驟與加熱試驗步驟，在200℃進行1分鐘的加熱，之後，冷卻後進行再度加熱，但與步驟分離前同樣地，黃色度b*的值快速地上升。 Further, for reference, in the comparative example, the separation oxidation step and the heating test step were performed at 200 ° C for 1 minute, and then cooled and then reheated, but the yellowness b* value was the same as before the step separation. Rise quickly.

接著，上述實施例的焊球，利用FE-AES(場發射式歐傑電子光譜)定量分析在200℃進行15分加熱的實施例1的焊球與在200℃進行30分鐘加熱的實施例2的焊球的氧化膜厚，並且根據連續電化學還原法(SERA，sequential electrochemical reduction analysis)進行定性分析，確認形成的氧化膜成分為Sn的氧化物(SnO及SnO2)。 Next, in the solder ball of the above embodiment, the solder ball of Example 1 which was heated at 200 ° C for 15 minutes by FE-AES (field emission type Auger electron spectrum) and Example 2 which was heated at 200 ° C for 30 minutes were quantitatively analyzed. The oxide film of the solder ball was thick, and qualitative analysis was performed by a sequential electrochemical reduction analysis (SERA) to confirm that the formed oxide film component was an oxide of Sn (SnO and SnO 2 ).

並且，以FE-AES實施定量分析的方式，因為SERA的分析數值容易分散，雖然定性分析是可能的，但作為可具體定量分析氧化膜厚之討論而言，還是以FE-AES分析的方式，容易顯示固定值。氧化膜的膜厚是以下的裝置及條件測定。並且，氧化膜厚的測定值為依據SiO2換算求得。 Moreover, the quantitative analysis by FE-AES, because the analytical value of SERA is easy to disperse, although qualitative analysis is possible, as a specific quantitative analysis of the thickness of the oxide film, it is still analyzed by FE-AES. It is easy to display a fixed value. The film thickness of the oxide film was measured by the following apparatus and conditions. Further, the measured value of the oxide film thickness was obtained in terms of SiO 2 conversion.

測定裝置：ULVAC-PHI，INC製，掃瞄型FE歐傑電子分光分析裝置。 Measuring device: ULVAC-PHI, INC, scanning type FE Oujie electronic spectroscopic analyzer.

測定條件：Beam Voltage：10kV，樣品電流：10nA(使用Ar離子槍的濺鍍深度的測定方法，以ISO/TR 15969為準則)。 Measurement conditions: Beam Voltage: 10 kV, sample current: 10 nA (measurement method of sputtering depth using an Ar ion gun, based on ISO/TR 15969).

表2顯示氧化膜厚和黃色度的測定結果。 Table 2 shows the results of measurement of oxide film thickness and yellowness.

如表2所示，可知氧化膜厚抑制至5nm以下，覆蓋層的膜厚可知較佳為4.5nm以下。再者，可知黃色度抑制在10以下，從表2的結果來看，可知5.7以下較佳。 As shown in Table 2, it is understood that the thickness of the oxide film is suppressed to 5 nm or less, and the film thickness of the coating layer is preferably 4.5 nm or less. Further, it is understood that the yellowness is suppressed to 10 or less, and from the results of Table 2, it is understood that 5.7 or less is preferable.

其次，以上述的實施例和比較例的焊球，製造膜厚、黃色度的變更品，檢驗保存性和濕潤性。 Next, the film thickness and the yellowness of the modified product were produced by the solder balls of the above-described examples and comparative examples, and the storage stability and wettability were examined.

各實施例的焊球，膜厚為4.5nm以下，實施例1的焊球，膜厚為2.6nm，實施例2的焊球，膜厚為4.1nm，實施例3的焊球，膜厚為1.5nm。 The solder balls of the respective examples have a film thickness of 4.5 nm or less, the solder balls of the first embodiment have a film thickness of 2.6 nm, and the solder balls of the second embodiment have a film thickness of 4.1 nm. The solder balls of the third embodiment have a film thickness of 1.5nm.

再者，各實施例的焊球，黃色度為5.7以下，實施例1的焊球，黃色度為4.60，實施例2的焊球，黃色度為5.77，實施例3的焊球，黃色度為3.90。 Further, the solder balls of the respective examples have a yellowness of 5.7 or less, the solder balls of the first embodiment have a yellowness of 4.60, and the solder balls of the second embodiment have a yellowness of 5.77. The solder balls of the third embodiment have a yellowness of yellow. 3.90.

另一方面，各比較例的焊球，膜厚為10nm以上，再者，黃色度為10以下，比較例1的焊球，黃色度為10.21，比較例2的焊球，黃色度為13.15。 On the other hand, in the solder balls of the comparative examples, the film thickness was 10 nm or more, and the yellowness was 10 or less. The solder ball of Comparative Example 1 had a yellowness of 10.21, and the solder ball of Comparative Example 2 had a yellowness of 13.15.

檢驗結果顯示於表3 The test results are shown in Table 3.

如表3所示，實施例1至實施例3的焊球，不論哪一個的保存性及濕潤性都滿足既定的條件，另一方面，各比較例的焊球，不論是保存性或是濕潤性，都不能滿足既定的條件。 As shown in Table 3, the solder balls of Examples 1 to 3 satisfy the predetermined conditions regardless of the storage stability and wettability, and on the other hand, the solder balls of the respective comparative examples are either preserved or wet. Sex, can not meet the established conditions.

因此，可知覆蓋層的厚度大於0nm、4.5nm以下，黃色度b*為5.7以下的焊球，無論保存性及濕潤性都提升。 Therefore, it is understood that the thickness of the coating layer is greater than 0 nm and 4.5 nm, and the solder ball having a yellowness b* of 5.7 or less is improved in both storage stability and wettability.

並且，關於本發明的焊接材料，能夠以焊膏電性接合於電極，可使用於電子元件的焊接接頭。 Further, the solder material of the present invention can be electrically bonded to the electrode with a solder paste, and can be used for a solder joint of an electronic component.

1A‧‧‧焊球 1A‧‧‧ solder balls

2‧‧‧焊接層 2‧‧‧welding layer

3‧‧‧覆蓋層 3‧‧‧ Coverage

3a‧‧‧SnO膜 3a‧‧‧SnO film

3b‧‧‧SnO2膜 3b‧‧‧SnO 2 film

Claims (10)

一種焊接材料，其特徵為包括：焊接層，由Sn含量為40%以上的合金構成的金屬材料或是由Sn含量為100%的金屬材料構成；以及覆蓋層，覆蓋上述焊接層表面之直徑1~1000μm的球體，上述覆蓋層為在上述焊接層的外側形成SnO膜、在上述SnO膜的外側形成SnO2膜，上述覆蓋層的厚度為大於Onm、4.5nm以下。 A solder material comprising: a solder layer, a metal material composed of an alloy having a Sn content of 40% or more or a metal material having a Sn content of 100%; and a cover layer covering a diameter of the surface of the solder layer 1 In the spherical body of 1000 nm, the cover layer is formed by forming a SnO film on the outer side of the solder layer, and forming a SnO 2 film on the outer side of the SnO film. The thickness of the cover layer is greater than Onm and 4.5 nm or less. 如申請專利範圍第1項所述之焊接材料，其中在L*a*b*表色系統中的黃色度為5.7以下。 The welding material according to claim 1, wherein the yellowness in the L*a*b* color system is 5.7 or less. 一種焊接材料，其特徵為包括：焊接層，由Sn的含量為40%以上的合金所構成的金屬材料或由Sn的含量為100%的金屬材料所構成的；以及覆蓋層，覆蓋上述焊接層表面之直徑1~1000μm的球體，上述覆蓋層為上述焊接層的外側形成SnO膜、在上述SnO膜的外側形成SnO2膜；該焊接材料的L*a*b*表色系統中的黃色度為5.7以下。 A solder material comprising: a solder layer, a metal material composed of an alloy having a Sn content of 40% or more or a metal material having a Sn content of 100%; and a cover layer covering the solder layer a sphere having a surface diameter of 1 to 1000 μm, wherein the coating layer forms a SnO film on the outer side of the solder layer, and a SnO 2 film is formed on the outer side of the SnO film; the yellowness in the L*a*b* color system of the solder material It is 5.7 or less. 如申請專利範圍第1~3項中任一項所述之焊接材料，其中上述焊接層含有Ag為0%以上、小於4%，Cu為0%以上、小於1%、P為0ppm以上、小於5ppm、Ge為0ppm以上、小於20ppm。 The solder material according to any one of claims 1 to 3, wherein the solder layer contains Ag of 0% or more and less than 4%, Cu of 0% or more, less than 1%, P of 0 ppm or more, and less than 5 ppm and Ge are 0 ppm or more and less than 20 ppm. 如申請專利範圍第1~4項中任一項所述之焊接材料，其中上述焊接層以使Sn含量成為40%以上的方式，(i)從Ni、Co、Fe、Sb之中選擇至少一個元素，使其含有 整體為1%以下或者是各別元素為小於1%，以及，從In、Bi選擇至少一個以上元素，使其含有整體為40%以下，或者是In、Bi其中一個元素為小於40%，另一個元素為小於20%，或者是：(ii)從Ni、Co、Fe、Sb之中選擇至少一個元素，使其含有整體為小於1%，或者是各別元素為小於1%，或是，從In、Bi之中選擇至少一個以上元素，使其含有整體為小於40%或者是In、Bi其中一個元素為小於40%，另一個元素為小於20%。 The welding material according to any one of claims 1 to 4, wherein the solder layer has a Sn content of 40% or more, (i) at least one selected from the group consisting of Ni, Co, Fe, and Sb. Element to make it contain The whole is 1% or less or the individual elements are less than 1%, and at least one or more elements are selected from In and Bi so as to contain 40% or less of the whole, or one of In and Bi is less than 40%, and the other element is less than 40%. One element is less than 20%, or: (ii) at least one element selected from Ni, Co, Fe, Sb, such that it contains less than 1% overall, or less than 1% of each element, or At least one or more elements are selected from In and Bi such that they contain less than 40% overall or one of In, Bi is less than 40%, and the other element is less than 20%. 如申請專利範圍第1~5項中任一項所述之焊接材料，其中放射的α線量為0.0200cph/cm2以下。 The welding material according to any one of claims 1 to 5, wherein the amount of α-ray emitted is 0.0200 cph/cm 2 or less. 一種焊接接頭，其特徵在於使用如申請專利範圍第1~6項中任一項所述之焊接材料而得到。 A welded joint obtained by using the welding material according to any one of claims 1 to 6. 一種焊接材料的製造方法，其特徵在於包括：由Sn含量為40%以上的合金構成的金屬材料或是由Sn含量為100%的金屬材料構成的焊接層之焊接層的形成步驟；在上述焊接層的外側形成SnO膜、在上述SnO膜的外側形成SnO2膜之厚度大於0nm、4.5nm以下的覆蓋層形成於上述焊接層的表面的氧化膜形成步驟以製造直徑為1~1000μm的球體。 A method for producing a solder material, comprising: a metal material composed of an alloy having a Sn content of 40% or more; or a solder layer forming step of a solder layer composed of a metal material having a Sn content of 100%; An SnO film is formed on the outer side of the layer, and a coating layer having a thickness of the SnO 2 film of more than 0 nm and 4.5 nm or less on the outer surface of the SnO film is formed on the surface of the solder layer to form a sphere having a diameter of 1 to 1000 μm. 如申請專利範圍第8項所述之焊接材料的製造方法，其中在上述氧化膜形成步驟，形成上述覆蓋層表面的L*a*b*表色系統中黃色度為5.7以下。 The method for producing a solder material according to claim 8, wherein in the oxide film forming step, the yellowness of the L*a*b* color system forming the surface of the cover layer is 5.7 or less. 如申請專利範圍第8項或第9項所述之焊接材料的製造方 法，其中在上述氧化膜的形成步驟，照射O2-Ar電漿於上述焊接層的表面。 The method for producing a solder material according to the above aspect of the invention, wherein in the forming step of the oxide film, an O 2 -Ar plasma is irradiated onto the surface of the solder layer.
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